Crystalline silicophosphoaluminate (MCM-10)

ABSTRACT

A new crystalline silicophosphoaluminate molecular sieve designated MCM-10 and having a particular crystal structure is provided. This crystalline material has ion-exchange properties and is readily convertible to catalytically active material.

CROSS-REFERENCE TO RELATED APPLICATION

This is a continuation-in-part of application Ser. No. 562,909, filedDec. 19, 1983, now abandoned.

BACKGROUND OF THE INVENTION

1. Field of the Invention

This invention relates to a novel synthetic crystallinesilicophosphoaluminate molecular sieve material, hereinafter "MCM-10",containing aluminum, silicon and phosphorus in its framework, and to usethereof in catalytic conversion of organic compounds. The crystallinematerial of this invention exhibits ion-exchange properties and caneasily be converted to catalytically active material.

2. Description of Prior Art

Zeolitic materials, both natural and synthetic, have been demonstratedin the past to have catalytic properties for various types ofhydrocarbon conversion. Certain zeolitic materials are ordered, porouscrystalline aluminosilicates having a definite crystalline structure asdetermined by X-ray diffraction, within which there are a large numberof smaller cavities which may be interconnected by a number of stillsmaller channels or pores. These cavities and pores are uniform in sizewithin a specific zeolitic material. Since the dimensions of these poresare such as to accept for adsorption molecules of certain dimensionswhile rejecting those of larger dimensions, these materials have come tobe known as "molecular sieves" and are utilized in a variety of ways totake advantage of these properties.

Such molecular sieves, both natural and synthetic, include a widevariety of positive ion-containing crystalline aluminosilicates. Thesealuminosilicates can be described as rigid three-dimensional frameworksof SiO₄ and AlO₄ in which the tetrahedra are cross-linked by the sharingof oxygen atoms whereby the ratio of the total aluminum and siliconatoms to oxygen atoms is 1:2. The electrovalence of the tetrahedracontaining aluminum is balanced by the inclusion in the crystal of acation, for example an alkali metal or an alkaline earth metal cation.This can be expressed wherein the ratio of aluminum to the number ofvarious cations, such as Ca/2, Sr/2, Na, K or Li, is equal to unity. Onetype of cation may be exchanged either entirely or partially withanother type of cation utilizing ion exchange techniques in aconventional manner. By means of such cation exchange, it has beenpossible to vary the properties of a given aluminosilicate by suitableselection of the cation. The spaces between the tetrahedra are occupiedby molecules of water prior to dehydration.

Prior art techniques have resulted in the formation of a great varietyof synthetic zeolites. The zeolites have come to be designated by letteror other convenient symbols, as illustrated by zeolite A (U.S. Pat. No.2,882,243), zeolite X (U.S. Pat. No. 2,882,244), zeolite Y (U.S. Pat.No. 3,130,007), zeolite ZK-5 (U.S. Pat. No. 3,247,195), zeolite ZK-4(U.S. Pat. No. 3,314,752), zeolite ZSM-5 (U.S. Pat. No. 3,702,886),zeolite ZSM-11 (U.S. Pat. No. 3,709,979) zeolite ZMS-12 (U.S. Pat. No.3,832,449), zeolite ZSM-20 (U.S. Pat. No. 3,972,983), zeolite ZSM-35(U.S. Pat. No. 4,016,245), zeolite ZSM-38 (U.S. Pat. No. 4,046,859), andzeolite ZSM-23 (U.S. Pat. No. 4,076,842) merely to name a few.

The crystalline silicophosphoaluminate of the present invention is notan aluminosilicate zeolite, but it is a molecular sieve material with anordered pore structure which accepts certain molecules while rejectingothers.

Aluminum phosphates are taught in U.S. Pat. Nos. 4,310,440 and4,385,994, for example. Aluminum phosphate materials have electroneutrallattices and, therefore, are not useful as ion-exchangers or as catalystcomponents. U.S. Pat. No. 3,801,704 teaches an aluminum phosphatetreated in a certain way to impart acidity.

The phosphorus-substituted zeolites of Canadian Pat. Nos. 911,416;911,417 and 911,418 are referred to as "aluminosilicophosphate"zeolites. Some of the phosphorus therein appears to be occluded, notstructural.

U.S. Pat. No. 4,363,748 describes a combination of silica andaluminum-calcium-cerium phosphate as a low acid activity catalyst foroxidative dehydrogenation. Great Britain Pat. No. 2,068,253 discloses acombination of silica and aluminum-calcium-tungsten phosphate as a lowacid activity catalyst for oxidative dehydrogenation. U.S. Pat. No.4,228,036 teaches an alumina-aluminum phosphate-silica matrix as anamorphous body to be mixed with zeolite for use as cracking catalyst.U.S. Pat. No. 3,213,035 teaches improving hardness of aluminosilicatecatalysts by treatment with phosphoric acid. The catalysts areamorphous.

U.S. Pat. No. 2,876,266 describes an active silicophosphoric acid orsalt phase of an amorphous material prepared by absorption of phosphoricacid by premolded silicates or aluminosilicates.

Aluminum phosphates are well known in the art as exemplified by U.S.Pat. Nos. 4,365,095; 4,361,705; 4,222,896; 4,210,560; 4,179,358;4,158,621; 4,071,471; 4,014,945; 3,904,550 and 3,697,550. Since theirneutral framework structure is void of ion-exchange properties, they areused as catalyst supports or matrices. The crystallinesilicophosphoaluminate synthesized hereby is a molecular sieve frameworkexhibiting ion-exchange properties and is easily and convenientlyconverted to material having intrinsic catalytic activity.

U.S. Pat. No. 4,440,871 teaches various silicoaluminophosphatematerials, none of which exhibit the structure of MCM-10.

SUMMARY OF THE INVENTION

The present invention is directed to a novel synthetic crystallinesilicophosphoaluminate molecular sieve material, hereinafter designated"MCM-10", containing aluminum, silicon and phosphorus in its framework,and to its use as a catalyst component in catalytic conversion oforganic, e.g hydrocarbon, compounds.

The anhydrous crystalline MCM-10 has the general formula:

    M.sub.x/m.sup.m+ :(AlO.sub.2).sub.1-y.sup.- :(PO.sub.2).sub.1-x.sup.+ :(SiO.sub.2).sub.x+y :N.sub.y/n.sup.n-

wherein M is a cation of valence m, N is an anion of valence n, and xand y are numbers of from greater than -1 to less than +1 which satisfythe relationships:

(1) is x is 0, then y is not 0,

(2) if y is 0, then x is not 0,

(3) if the atomic ratio of Al/P is greater than 1, then (x+y) is greaterthan 0.001 and y+0.6x is less than 0.4, and

(4) if the atomic ratio of Al/P is less than 1, then (x+y) is greaterthan 0.001 and x+0.5y is less than 0.5.

In the composition above, when x is greater than y thesilicophosphoaluminate is a cation exchanger with potential use as anacidic catalyst. When x is less than y, the silicophosphoaluminate is ananion exchanger with potential use as a basic catalyst. Such MCM-10crystalline material has the characteristic x-ray diffraction pattern,in its calcined form, as set forth in Table 1-B hereinafter.

In the as synthesized form of the MCM-10, the silicophosphoaluminate canalso contain occluded organic material, A, and water molecules,entrapped during the synthesis and filling the microporous voids. Itthen has the general formula:

    vA:M.sub.x/m.sup.m+ :(AlO.sub.2).sub.1-y.sup.- :(PO.sub.2).sub.1-x.sup.+ :(SiO.sub.2).sub.x+y :N.sub.y/n.sup.n- :w(H.sub.2 O)

wherein v is the number of moles of A, occluded organic materialresulting from organic directing agent and/or solvent used in synthesisof and filling microporous voids of the MCM-10, which material may beremoved upon calcination, w is moles of H₂ O, e.g. from 0 to about 5,and x and y are the numbers defined hereinafter. The MCM-10 crystallinematerial in the as-synthesized form has the characteristic x-raydiffraction patter a set forth in Table 1-A hereinafter.

The crystalline silicophosphoaluminate of this invention is a uniquecomposition of matter which exhibits a valuable combination of catalyticsorption and ion-exchange properties which distinguishes it from knownaluminum phosphates.

EMBODIMENTS

The disclosure of U.S. application Ser. No. 562,909 is incorporatedherein by reference.

The silicophosphoaluminate material of the present invention willexhibit unique and useful catalytic, sorptive and shape selectiveproperties along with a silicon/(aluminum+phosphorus) atomic ratio ofless than unity, e.g. from about 0.001 to about 0.99. If synthesizedwith an aluminum/phosphorus atomic ratio of greater than one, thecrystalline silicophosphoaluminate exhibits an aluminum/silicon atomicratio of greater than 1.5, and usually in the range from 1.6 to 600.When the aluminum/phosphorus atomic ratio is of less than one, itexhibits a phosphorus/silicon atomic ratio of greater than unity,usually within the range from 1.2 to 600. It is well recognized thataluminum phosphates exhibit a phosphorus/aluminum atomic ratio of only0.8 to 1.2 and contain no silicon. Also, the phosphorus-substitutedzeolite compositions, sometimes referred to as "aluminosilicophosphatezeolites", have a silicon/aluminum atomic ratio of from 0.66 to 8.0, anda phosphorus/aluminum atomic ratio of from greater than 0 to 1.0.

The original cations of the as synthesized MCM-10 can be replaced inaccordance with techniques well known in the art, at least in part, byion exchange with other cations. Preferred replacing cations includemetal ions, hydrogen ions, hydrogen precursor, e.g., ammonium, ions andmixtures thereof. Particularly preferred cations are those which renderthe MCM-10 catalytically active, especially for hydrocarbon conversion.These include hydrogen, rare earth metal and metals of Groups IA, IIA,IIIA, IVA, IB, IIB, IIIB, IVB, VIB and VIII of the Periodic Table of theElements.

Typical ion exchange techniques would be to contact the synthetic MCM-10with a salt of the desired replacing cation or cations. Examples of suchsalts include the halides, e.g. chlorides, nitrates and sulfates.

The crystalline MCM-10 of the present invention can be beneficiallythermally treated, either before or after ion exchange. This thermaltreatment is performed by heating the silicophosphoaluminate in anatmosphere such as air, nitrogen, hydrogen, steam, etc., at atemperature of from about 300° C. to about 1100° C., preferably fromabout 350° to about 750° C., for from about 1 minute to about 20 hours.While subatmospheric or superatmospheric pressures may be used for thisthermal treatment, atmospheric pressure is desired for reasons ofconvenience.

MCM-10 exhibits a definite X-ray diffraction pattern which distinguishesit from other crystalline materials. The X-ray diffraction pattern ofthe as synthesized MCM-10 has the following characteristic values:

                  TABLE 1-A    ______________________________________    Intracrystalline d-Spacings(A)                       Relative Intensities    ______________________________________    11.85 ± 0.1     w    10.20 ± 0.1     s-vs    7.65 ± 0.05     vs    6.86 ± 0.05     m    5.93 ± 0.05     w    5.67 ± 0.05     m    5.11 ± 0.05     s    5.01 ± 0.05     s    4.49 ± 0.05     w    4.37 ± 0.05     vs    4.09 ± 0.05     vs    3.95 ± 0.03     w    3.80 ± 0.03     m    3.73 ± 0.03     w    3.43 ± 0.03     m    3.22 ± 0.03     m    3.16 ± 0.03     w    2.99 ± 0.02     w    2.97 ± 0.02     w    2.93 ± 0.02     m    2.85 ± 0.02     m    2.75 ± 0.02     w    2.68 ± 0.02     m    2.59 ± 0.02     w    ______________________________________

Table 1-B lists the characteristic diffraction lines of the calcined(450° C., atmospheric pressure, 4 hours) form of MCM-10.

                  TABLE 1-B    ______________________________________    Intracrystalline d-Spacing (A)                       Relative Intensities    ______________________________________    11.75 ± 0.1     w    10.11 ± 0.1     vs    7.56 ± 0.05     vs    6.81 ± 0.05     s    5.65 ± 0.05     m    5.08 ± 0.05     m    4.94 ± 0.05     vs-s    4.46 ± 0.05     w    4.35 ± 0.05     vs    4.28 ± 0.05     m    4.08 ± 0.05     vs    3.85 ± 0.03     w    3.75 ± 0.03     w    3.41 ± 0.03     m    3.18 ± 0.03     s    2.96 ± 0.02     m    2.92 ± 0.02     m    2.88 ± 0.02     w    2.83 ± 0.02     m    2.66 ± 0.02     m    2.58 ± 0.02     w    ______________________________________

These X-ray diffraction data were collected with a Rigaku X-ray system,using copper K-alpha radiation. The positions of the peaks, expressed indegrees 2 theta, where theta is the Bragg angle, were determined bystep-scanning at 0.02 degrees of 2 theta intervals and a counting timeof 1 second for each step. The interplanar spacings, d, measured inAngstrom units (A), and the relative intensities of the lines,I/I_(o),where I_(o) is one-hundredth of the intensity of the strongestline, including subtraction of the background, were derived with the useof a profile fitting routine. The relative intensities are given interms of the symbols vs=very strong (75-100%), s=strong (50-74%),m=medium (25-49%) and w=weak (0-24%). It should be understood that thisX-ray diffraction pattern is characteristic of all the species of MCM-10compositions synthesized by the present invention. Ion exchange ofcations with other ions results in a silicophosphoaluminate whichreveals substantially the same X-ray diffraction pattern with some minorshifts in interplanar spacing and variation in relative intensity. Othervariations can occur, depending on the silicon/aluminum andphosphorus/aluminum ratios of the particular sample, as well as itsdegree of thermal treatment.

The crystalline MCM-10 material of this invention may be converted tothe dry, hydrogen form by the above thermal treatment of the organiccation-containing form or hydrogen ion precursor-containing formresulting from ion exchange.

In general, the silicophosphoaluminate of the present invention can beprepared from a two-phase reaction mixture containing sources ofaluminum, phosphorus and silicon, directing agent(s) and a substantiallywater immiscible organic solvent. The overall molar composition of thetwo-phase synthesis mixture is in terms of oxides and organiccomponents:

    (A).sub.a :(M.sub.2 O).sub.b :(Al.sub.2 O.sub.3).sub.c :(SiO.sub.2).sub.d :(P.sub.2 O.sub.5).sub.e :(Solvent).sub.f :(anion source).sub.g (H.sub.2 O).sub.h

where a/(c+d+e) is less than 4, b/(c+d+e) is less than 2, d/(c+e) isless than 2, f/(c+d+e) is from 0.1 to 15, g/(c+d+e) is less than 2 andh/(c+d+e) is from 3 to 150. The "Solvent" is an organic solvent and "A"is any organic compound or material such as that derived from an organicdirecting agent or organic solvent. The anion is not necessarilyseparately added to the two-phase system, but may or may not appear inthe product crystals from one or more of the other component sources.

Reaction conditions consist of carefully heating the foregoing reactionmixture at a rate of from 5° C. to 200° C. per hour to a temperature offrom about 80° C. to about 300° C. for a period of time of from about 5hours to about 500 hours until crystals of MCM-10 are formed. A morepreferred temperature range is from about 100° C. to about 200° C. withthe amount of time at a temperature in such range being from about 24hours to about 168 hours. During heating and maintaining the reactionmixture at the desired temperature, the pH must be carefully controlledto be from about 2 to about 9. Control of pH can be accomplished byadjusting the concentration of the added organic and/or inorganicbase(s).

The reaction is carried out until crystals of the desired MCM-10 form.The crystalline product is recovered by separating same from thereaction medium, as by cooling the whole to room temperature, filteringand washing with water before drying.

The above reaction mixture composition can be prepared utilizingmaterials which supply the appropriate components. The aqueous phasecomponents may include from the sources of the elements silicon,phosphorus, or aluminum, those not included in the organic phase. Theorganic phase comprises an organic solvent and a source of at least oneof the elements silicon, phosphorus, or aluminum insoluble in theaqueous phase under reaction conditions. The aqueous phase also containsthe required organic and/or inorganic directing agent(s).

The useful sources of aluminum, as non-limiting examples, include anyknown form of aluminum oxide or hydroxide, organic or inorganic salt orcompound. The useful sources of silicon include, as non-limitingexamples, any known form of silicon dioxide or silicic acid, alkoxy- orother compounds of silicon. The useful sources of phosphorus include, asnon-limiting examples, any known form of phosphorus acids or phosphorusoxides, phosphates and phosphites, and organic derivates of phosphorus.

The organic solvent is a C₅ -C₁₀ alcohol or any other liquid organiccompound substantially immiscible with water, as non-limiting examples.

The organic directing agent can be selected from the group consisting oforganic mono-, di- or polyamines and onium compounds having thefollowing formula:

    R.sub.4 M.sup.+ X.sup.- or (R.sub.3 M.sup.+ R'M.sup.+ R.sub.3)X.sub.2

wherein R or R' is alkyl of from 1 to 20 carbon atoms, heteroalkyl offrom 1 to 20 carbon atoms, aryl, heteroaryl, cycloalkyl of from 3 to 6carbon atoms, cycloheteroalkyl of from 3 to 6 carbon atoms, orcombinations thereof; M is a tetracoordinate element (e.g. nitrogen,phosphorus, arsenic, antimony or bismuth) or a heteroatom (e.g. N, O, S,Se, P, As, etc.) in an alicyclic, heteroalicyclic or heteroaromaticstructure; and X is an anion (e.g. fluoride, chloride, bromide, iodide,hydroxide, acetate, sulfate, carboxylate, etc.). When M is a heteroatomin an alicyclic, heteroalicyclic or heteroaromatic structure, suchstructure may be, as non-limiting examples, ##STR1## wherein R' is alkylof from 1 to 20 carbon atoms, heteroalkyl of from 1 to 20 carbon atoms,aryl, heteroaryl, cycloalkyl of from 3 to 6 carbon atoms orcycloheteroalkyl of from 3 to 6 carbon atoms.

Particularly preferred directing agents for the present method includeonium compounds, above defined, wherein R is alkyl of 1 to 4 carbonatoms, M is nitrogen and X is halide or hydroxide. Non-limiting examplesof these include tetrapropylammonium hydroxide, tetraethylammoniumhydroxide and tetrapropylammonium bromide. An inorganic hydroxide orsalt of suitable composition can also be used as a supplementaldirecting agent non-limiting examples of which are CsOH and KOH, CsCland KCl.

The MCM-10 crystals prepared by the instant invention can be shaped intoa wide variety of particle sizes. Generally speaking, the particles canbe in the form of a powder, a granule, or a molded product, such as anextrudate having particle size sufficient to pass through a 2 mesh(Tyler) screen and be retained on a 400 mesh (Tyler) screen. In caseswhere the catalyst is molded, such as by extrusion, the crystals can beextruded before drying or partially dried and then extruded.

It may be desired to incorporate the new MCM-10 crystal with anothermaterial, i.e., a matrix, resistant to the temperatures and otherconditions employed in various organic conversion processes. Suchmaterials include active and inactive material and synthetic ornaturally occurring zeolites as well as inorganic materials such asclays, silica and/or metal oxides, e.g. alumina. The latter may beeither naturally occurring or in the form of gelatinous precipitates orgels including mixtures of silica and metal oxides. Catalystcompositions containing the MCM-10 crystals will generally comprise fromabout 1% to 90% by weight of the MCM-10 material and from about 10% to99% by weight of a matrix material. More preferably, sole catalystcompositions will comprise from about 2% to 80% by weight of the MCM-10material and from about 20% to 98% by weight of the matrix.

Use of a material in conjunction with the new MCM-10 crystal, i.e.combined therewith, which is active, tends to alter the conversionand/or selectivity of the overall catalyst in certain organic conversionprocess. Inactive materials suitably serve as diluents to control theamount of conversion in a given process so that products can be obtainedeconomically and orderly without employing other means for controllingthe rate of reaction. These materials may be incorporated into naturallyoccurring clays, e.g. bentonite and kaolin, to improve the crushstrength of the catalyst under commercial operating conditions. Saidmaterials, i.e. clays, oxides, etc., function as binders for thecatalyst. It may be desirable to provide a catalyst having good crushstrength because in commercial use it is desirable to prevent thecatalyst from breaking down into powder-like materials. These claybinders have been employed normally only for the purpose of improvingthe crush strength of the overall catalyst.

Naturally occurring clays which can be composited with the new crystalinclude the montmorillonite and kaolin families which include thesubbentonites, and the kaolins commonly known as Dixie, McNamee, Georgiaand Florida clays or others in which the main mineral constituent ishalloysite, kaolinite, dickite, nacrite, or anauxite. Such clays can beused in the raw state as originally mined or initially subjected tocalcination, acid treatment or chemical modification.

In addition to the foregoing materials, the crystalline MCM-10 can becomposited with a porous matrix material such as aluminum phosphate,silica-alumina, silica-magnesia, silica-zirconia, silica-thoria,silica-beryllia, silica-titania as well as ternary compositions such assilica-alumina-thoria, silica-alumina-zirconia silica-alumina-magnesiaand silica-magnesia-zirconia. The relative proportions of finely dividedcrystalline material and inorganic oxide gel matrix vary widely, withthe crystal content ranging from about 1 to about 90 percent by weightand more usually, particularly when the composite is prepared in theform of beads, in the range of about 2 to about 80 weight percent of thecomposite.

Employing a catalytically active form of the novel MCM-10 material ofthis invention as a catalyst component, said catalyst possiblycontaining additional hydrogenation components, reforming stocks can bereformed employing a temperature of from about 370° C. to about 540° C.,a pressure of from about 100 psig to about 1000 psig, (791 to 6996 KPa)preferably from about 200 psig to about 700 psig, (1480 to 4728 KPa) aliquid hourly space velocity is from about about 0.1 to about 10,preferably from about 0.5 to about 4, and a hydrogen to hydrocarbon moleratio of from about 1 to about 20, preferably from about 4 to about 12.

A catalyst comprising the present MCM-10 molecular sieve can also beused for hydroisomerization of normal paraffins, when provided with ahydrogenation component, e.g. platinum. Such hydroisomerization iscarried out at a temperature of from about 90° C. to about 375° C.,preferably from about 145° C. to about 290° C., with a liquid hourlyspace velocity of from about 0.01 to about 2, preferably from about 0.25to about 0.50, and with a hydrogen to hydrocarbon mole ratio of fromabout 1:1 to about 5:1. Additionally, such a catalyst can be used forolefin or aromatic isomerization, employing a temperature of from about200° C. to about 480° C.

Such a catalyst can also be used for reducing the pour point of gasoils. This reaction is carried out at a liquid hourly space velocity offrom about 10 to about 30 and at a temperature of from about 425° C. toabout 595° C.

Other reactions which can be accomplished employing a catalystcomprising the MCM-10 of this invention containing a metal, e.g.platinum, include hydrogenation-dehydrogenation reactions anddesulfurization reactions, olefin polymerization (oligomerization) andother organic compound conversions, such as the conversion of alcohols(e.g. methanol) or ethers (e.g. dimethylether) to hydrocarbons, and thealkylation of aromatics (e.g. benzene) in the presence of an alkylatingagent (e.g. ethylene).

In order to more fully illustrate the nature of the invention and themanner of practicing same, the following examples are presented. In theexamples, whenever adsorption data are set forth for comparison ofsorptive capacities for various adsorbants, they were determined asfollows:

A weighed sample of the calcined adsorbant was contacted with a flowingstream of the equilibrium vapor of the adsorbate at 25° C., admixed withdry nitrogen. Adsorbates were water vapor and n-hexane, 2-methylpentane,xylene or cyclohexane vapors. The sample temperature was maintained at90° C. for adsorbates other than ortho-xylene for which it was 120° C.and water for which it was 60° C. . The increase in weight was measuredgravimetrically and converted to the adsorption capacity of the samplein weight percent of calcined adsorbant.

When Alpha Value is examined, it is noted that the Alpha Value is anapproximate indication of the catalytic cracking activity of thecatalyst compared to a standard catalyst and it gives the relative rateconstant (rate of normal hexane conversion per volume of catalyst perunit time). It is based on the activity of the highly activesilica-alumina cracking catalyst taken as an Alpha of 1 (RateConstant=0.016 sec⁻¹). In the case of zeolite HZSM-5, only 174 ppm oftetrahedrally coordinated Al₂ O₃ are required to provide an Alpha Valueof 1. The Alpha Test is described in U.S. Pat. No. 3,354,078 and in TheJournal of Catalysis, Vol. IV, pp. 522-529 (August 1965), eachincorporated herein by reference as to that description.

When ion-exchange capacity is examined, it is determined by titratingwith a solution of sulfamic acid the gaseous ammonia evolved during thetemperature programmed decomposition of the ammonium-form of thesilicophosphoaluminate. The method is described in Thermochimica Acta,Vol. III, pp. 113-124, 1971 by G. T. Kerr and A. W. Chester,incorporated herein by reference as to that description.

EXAMPLE 1

A two-phase synthesis reaction mixture was prepared with the organicphase comprised of 60 g n-hexanol and 10 g Si(OC₂ H₅)₄, and the aqueousphase comprised of 23.1 g H₃ PO₄ (85%), 10 g Al₂ O₃,

    154.4 g of 3.6N, Diquat-7 (OH).sub.2 (i.e. (OH)(CH.sub.3).sub.3 N(CH.sub.2).sub.7 N(CH.sub.3).sub.3 (OH)).

The reaction mixture as a whole had a composition including 10.8% Si,45% P and 44.2% Al, the percentages atomic. The directing agent wasDiquat-7 (OH)₂. The initial pH was slightly higher than 6.

The reaction mixture was heated at 50° C. per hour to 130° C. andmaintained at that temperature for 24 hours. It was then heated to 180°C. and maintained there for 144 hours. During this time, mixing wasobtained by spinning at 800 rpm.

The crystalline product was separated from the reaction mixture byfiltration, water washed and then dried at 80° C. The productcrystalline aluminophosphate had a composition including 19.9% Si, 37.1%P, and 43.0% Al, the percentages atomic. A sample of the as synthesizedsilicophosphoaluminate was then submitted for X-ray analysis. It wasfound to be a crystalline molecular sieve exhibiting the diffractionlines shown in Table 2.

                  TABLE 2    ______________________________________    Interplanar   Observed  Relative    d-Spacing (A) 2 × Theta                            Intensity, I/I.sub.o    ______________________________________    11.8446        7.457    17.04    10.1960        8.665    78.40    7.6489        11.559    84.85    6.8567        12.900    24.39    5.9273        14.934    13.31    5.6856        15.573    35.97    5.1059        17.354    57.48    5.0091        17.692    64.21    4.4885        19.763    10.91    4.3742        20.285    85.60    4.0918        21.701    100.00    3.9534        22.471    11.66    3.7982        23.402    42.70    3.7262        23.861    13.62    3.4249        25.995    26.69    3.2165        27.711    81.46    3.1626        28.193     8.65    2.9904        29.854    20.84    2.9657        30.108    21.06    2.9347        30.433    32.19    2.8448        31.420    36.84    2.7846        32.118     7.41    2.6813        33.390    42.38    2.5893        34.614    19.50    ______________________________________

EXAMPLE 2

The synthesis of Example 1 was repeated except that only 30 g of waterwas added. The resulting crystalline product silicophosphoaluminate hadan X-ray diffraction pattern showing lines similar to those reported inTable 2. The product was 50% crystalline.

EXAMPLE 3

A quantity of the crystalline silicophosphoaluminate of Example 1 wascalcined at 450° C. in nitrogen for 4 hours and then X-ray analyzed. Theresults are presented in Table 3.

                  TABLE 3    ______________________________________    Interplanar   Observed  Relative    d-Spacing (A) 2 × Theta                            Intensity, I/I.sub.o    ______________________________________    11.7521        7.516    20.81    10.1070        8.742    85.44    7.5640        11.690    100.00    6.8057        12.997    71.80    5.6522        15.665    25.38    5.0770        17.453    29.02    4.9416        17.935    78.18    4.4564        19.907    16.58    4.3515        20.392    99.63    4.2756        20.758    25.68    4.0759        21.787    83.25    3.8546        23.055    15.88    3.7499        23.707    21.15    3.4089        26.119    42.38    3.1778        28.056    68.19    2.9616        30.151    29.91    2.9230        30.558    51.09    2.8835        30.988    10.99    2.8321        31.564    36.78    2.6565        33.711    43.09    2.5795        34.749    19.66    ______________________________________

EXAMPLE 4

A sample of the calcined product silicophosphoaluminate of Example 3 wasevaluated for sorption properties to confirm its molecular sieve nature.The results in weight percent indicating shape selectivity were asfollows:

hexane (90° C.): 4.75

cyclohexane (90° C.): 2.05

EXAMPLE 5

A quantity of the crystalline silicophosphoaluminate of Example 1 wascalcined as described in Example 3 and ammonium-exchanged using anaqueous solution of 1M NH₄ NO₃. The ion-exchange capacity measured fromthe evolution of ammonia was determined to be 1.51 meq/g.

What is claimed is:
 1. A synthetic crystalline material having acomposition as follows:

    vA:M.sub.x/m.sup.m+ :(AlO.sub.2).sub.1-y.sup.- :(PO.sub.2).sub.1-x.sup.+ :(SiO.sub.2).sub.x+y :N.sub.y/n.sup.n- w:(H.sub.2 O

wherein M is a cation of valence m, N is an anion of valence n, A isoccluded organic directing agent and solvent, v is the number of molesof A, w is the number of moles of H₂ O and x and y are numbers of fromgreater than -1 to less than +1 which satisfy the relationships: (1) ifx is 0, then y is not 0, (2) if y is 0, then x is not 0, (3) if theatomic ratio of Al/P is greater than 1, then x+y is greater than 0.001and y+0.6x is less than 0.4, and (4) if the atomic ratio of Al/P is lessthan 1, then x+y is greater than 0.001 and x+0.5y is less than0.5,which, as synthesized, exhibits a characteristic X-ray diffractionpattern as shown in Table 1-A of the specification.
 2. The syntheticcrystalline material of claim 1 which, following calcination, exhibits acharacteristic X-ray diffraction pattern as shown in Table 1-B of thespecification.
 3. The synthetic crystalline material of claim 2 having acomposition in the anhydrous state as follows:

    M.sub.x/m.sup.m+ :(AlO.sub.2).sub.1-y.sup.- :(PO.sub.2).sub.1-x.sup.+ :(SiO.sub.2).sub.x+y :N.sub.y/n.sup.n-

wherein M is a cation of valence m, N is an anion of valence n, and xand y are numbers of from greater than -1 to less than +1 which satisfythe relationships: (1) if x is 0, then y is not 0, (2) if y is 0, then xis not 0, (3) if the atomic ratio of Al/P is greater than 1, then x+y isgreater than 0.001 and y+0.6x is less than 0.4, and (4) if the atomicratio of Al/P is less than 1, then x+y is greater than 0.001 and x+0.5yis less than 0.5.
 4. The crystalline material of claim 3 having cationsreplaced, at least in part, with a cation or a mixture of cationsselected from the group consisting of hydrogen and hydrogen precursors,rare earth metals and metals from Groups IA, IIA, IIIA, IVA, IB, IIB,IIIB, IVB, VIB and VIII of the Periodic Table of the Elements.
 5. Thecrystalline material resulting from thermal treatment of the crystallinematerial of claim
 4. 6. The crystalline material resulting from thermaltreatment of the crystalline material of claim
 1. 7. A catalystcomposition comprising from 1% to 90% by weight of the crystallinematerial of claim 1 and from 10% to 99% by weight of a matrix material.8. A catalyst composition comprising from 1% to 90% by weight of thecrystalline material of claim 2 and from 10% to 99% by weight of amatrix material.
 9. The crystalline material of claim 2 having cationsreplaced, at least in part, with a cation or a mixture of cationsselected from the group consisting of hydrogen and hydrogen precursors,rare earth metals and metals from Groups IA, IIA, IIIA, IVA, IB, IIB,IIIB, IVB, VIB and VIII of the Periodic Table of the Elements.
 10. Acatalyst composition comprising from 1% to 90% by weight of thecrystalline material of claim 9 and from 10% to 99% by weight of amatrix material.
 11. The crystalline material resulting from thermaltreatment of the crystalline material of claim
 9. 12. A catalystcomposition comprising from 1% to 90% by weight of the crystallinematerial of claim 11 and from 10% to 99% by weight of a matrix material.13. The crystalline material of claim 1 having cations replaced, atleast in part, with a cation or a mixture of cations selected from thegroup consisting of hydrogen and hydrogen precursors, rare earth metalsand metals from Groups IA, IIA, IIIA, IVA, IB, IIB, IIIB, IVB, VIB andVIII of the Periodic Table of the Elements.
 14. A catalyst compositioncomprising from 1% to 90% by weight of the crystalline material of claim13 and from 10% to 99% by weight of a matrix material.
 15. Thecrystalline material resulting from thermal treatment of the crystallinematerial of claim
 13. 16. A catalyst composition comprising from 1% to90% by weight of the crystalline material of claim 15 and from 10% to99% by weight of a matrix material.